Comparative Interpretation of Absorption Spectra of Technetium (IV) and Rhenium (IV) Hexahalides

Author:

Jørgensen Chr. Klixbüll1,Schwochau Klaus2

Affiliation:

1. 1Cyanamid European Research Institute, Cologny (Geneva), Switzerland

2. 2Arbeitsgruppe „Institut für Radiochemie“ der Kernforschungsanlage Jülich, at present situated in Institut für Kernchemie der Universität Köln, Germany

Abstract

Absorption spectra of aqueous solutions of TcX6- and ReX6- (X = F, Cl, Br, I) are measured between 8 000 and ∼ 50 000 cm-1 and theoretically discussed. The electron transfer spectra indicate the optical electronegativity xopt= 2.25 for Tc (IV) and 2.05 for the less oxidizing Re (IV). The spectrochemical parameter Δ is determined to 28 400 cm-1 in TcF6 and 32 800 cm-1 in ReF6-. The nephelauxetic effect is evaluated from the spin-forbidden intra-sub-shell transitions in all eight species, and from the two spin-allowed bands of TcF6- The vibrational structure of the narrow absorption bands and the possible weak distortion from octahedral symmetry of Tc (IV) hexahalides are discussed.

Publisher

Walter de Gruyter GmbH

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy,Mathematical Physics

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